Gelatin subbing compositions containing an unsaturated lactone



Patented Feb. 8, 1949 UNITED sures osmium S'UBBIN-fi comro'sirxouscow TAINING'AN UNSATUR ATEDLAGTGNE Frank J. Kaszuba, Binghamkm, N. .,,.;assi;nor to General Aniline & Film Coronation. New York, N. Y., a corporation of Delaware No Drawing.

8 Claims.

with an organic solvent for the material of the film base, such as acetone, ethyl acetate, an alcohol-ether or an alcohol acetone mixture. Gelatinis insoluble in these organic solvents and the film base is insoluble in water, but it is possible to prepare dispersions consisting of gelatin in a mixture of one of the organic solvents and water with a volatile organic acid, such as acetic acid, and the like, as a dispersing agent.

Many volatile and non-volatile organic acids have heretofore been used as dispersing agents for the gelatin in subbing compositions. It has been found, however, that the use of these acids causes artificial ageing and a decrease in sensitivity of the gelatino silver-halide emulsion layer.

This efiect is due primarily to the acidic nature of the dispersing agent. Moreover, subbing solu tions containing a dispersing agent possessing acidic characteristics have a tendency to corrode the film-making machinery and the solventrecovery system which is customarily a part thereof.

The present invention has as an object to overcome the above-mentioned difiiculties and to provide a method of dispersing gelatin in a subhing composition by means of dispersing agents. which will not desensitize and artificially age the .gelatino silver-halide emulsion layer and which will not corrode thefilm makinsmachinersr or solvent recovery systemconnected therewith. Another object .is to provide av non-desensitizing, non-corrosive dispersing agent for gelatin in subbing compositions.

.Afurther object is to provide a new type of gel solution in .whichthe. gelatin is dispersed by means of a non-desensitizing, non corrosivc dis persing agent, which has no adverse e'fiect upon photographic gelatino silver-halide emulsions.

Other objects will appear from the following description.

These objects are accomplished by the 1.1%. as dispersing agents ingelatin subbing compositions.

Application December 18'. 1M8. Serial: No. 71.74093- ot-unsaturated last-om. Qhtt ctm cl-bi t e- 2b lowing-seneraii mulae wherein R. is-either hydrogen or a, methyl group. 'T'ypical unsaturated lactones corresponding to the foregoing general formulae, which are in chided within the scope of this invention, are as M Orotonolnctone' B Rec. (raw. China, to, K123 (192.1).

fi mise ice lac ose a Bed; 11. 24's.

wnzenemw amount or the above-nestle; 11111 4 2 4 rated laziness. swimmer be mem s: as dis pea-s ng ents. may vary ove a small r nge. such as. iorjmmple, new about 0.05% to 1%.:anti prefe ably from 111% to it? 9; gela in range Iron: about 0.5% to 1.5% and. x iiiimi' from 0.5% to 1.0%, and water iron; about mam -a mas organic solvent or mixture of such solvents may range from 94.5% to 98.5%. All proportions are by weight.

The subbing compositions are made by mixing the components in various ways so as to form a free flowing composition which dries or sets within a reasonable length of time and forms a thin layer on a film base. In general, it is desirable to dissolve the unsaturated lactone (dispersing agent) in water and add to it the gelatin until the gelatin is dispersed. Slight warming and agitation will facilitate the dispersion of the gelatin in the aqueous solution of the unsaturated lactone.

gelatin, and the solution thus ;'obtained is deposited on a film base in any convenient manner, such as by beading, immersion,'roll application, or otherwise, the subbing operation preferably being carried out in connection with, or as a part of, the process of making the-film support itself. The subbing solutions made up as above described are clear dispersions of gelatin in the solvent mixture. I

The film bases used in accordance with this in vention are the cellulose derivatives," '.-",'cellulose nitrate, cellulose acetate, and other lower fatty acid esters of cellulose including simple and mixed esters, such as cellulose propionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetate-butyrate and the like, ethers of cellulose, such as the ethyl-ether, benzyl ether, and the like, or of an film-forming polymer or resin, such as polyvinyl chloride, copolymers of vinyl chlorides and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, and the like, superpolymers as described in United States Patents 2,071,250, 2,071,252, 2,071,253 and 2,130,- 948.

It will be appreciated that each difierent type of cellulose ester, ether and mixtures thereof, including the synthetic linear superpolymers, requires a slightly different solvent or solvent combination. The solvent or solvent mixture employed does not dissolve gelatin, but must be such that it will have a solvent. or at least a softening or swelling action on the film base, so as to stick or anchor the gelatin upon the area of the base which has been softened or swollen, and the term "solvent as used in the claims should be so construed. For example, with a cellulose acetate or a superpolymer base glycerol-a-chlorohydrin, a low molecular weight alcohol, e. g., methanol, ethanol, and the like, or aketone, such as acetone, or a mixture of glycerol-a-chlorohydrin, alcohol and acetone may be employed. The ratio of al cohol to acetone ranges from about 25-75% to 75-25%, respectively. With cellulose acetatepropionate film base, an alkyl ester, such as, for example, methyl acetate, ethyl acetate, butyl acetate, and the like, either alone or with methanol, glycerol-a=chlorohydrinor .lA-dioxane, may be efiectively employed, The weight of glycerola-chlorohydrin employed may vary from 1% to 5%. It may be mentioned at this point that the -claims.should-be so construed. Sincethejmatdrials suitable for film base and their solvent prop} ertiesare' known, no difficulty is presented inseilecting a suitable solvent or solvent mixture for useinthe subbing compositions; v T-he invention will be further" illustrated." but The organic solvent or mixtures thereofare then mixed with the aqueous dispersion of.

is not intended to be limited by the following examples.

Example I A film base of cellulose acetate was coated with the following subbing solution:

After the subbing layer had dried, the usual light sensitiv emulsion layer was coated directly on it. After exposure and processing the emulsion adhered tenaciously to the cellulose acetate film support.

Example II Parts Gelatin 0.7 ,Water 2.1 a-Angelica lactone 0.2 Glycerol wchlorohydrin 2.0 Methanol 40.0 Acetone 55.0

After the subbing layer had dried, the usual light-sensitiv emulsion layer was coated directly on it. After exposure and processing the emulsion adhered tenaciously to the cellulose acetatepropionate film support.

Example III A film base prepared from poly (vinyl chloride vinyl acetate) was coated with the following sub- After the subbing layer had dried, the usual light-sensitive emulsion layer was coated directly on it. After exposure and processing, the emulsion adhered tenaciously to the syntheti linear superpolymer film support.

The specific coating solutions set forth in the above examples may be substituted by the following:

Example IV Parts Gelatin 'T. 0.5 Water 1.3 'AW-Crotonolactone 0.2 Ethanol 75.0 Acetone 23.0

'- Example Y r, Parts Gelatin 1.0 Water i 2.7 lit--Angelicalactone 0.3

160.0 Acetone' -L 36.0

The photographic film bases produced according'to -the present invention were found to be en,- tirely' satisfactory and to give the customary physical requirements, such as, extreme strength, flexibility, and good water-resistance.

The small quantity of the unsaturated lactone, which may remain with the gelatin after evaporation of the water and organic solvent from the subbing composition, has no adverse effect upon the light-sensitive emulsion layer, nor has the subbing composition any adverse effect upon the containers in which it is stored, or uponthe coating equipment employed.

It will be understood that wherein the claims appended hereto, the term subbing is used, that such is intended to include the operation of applying a subbing layer from any one of the subbing compositions prepared in accordance with the present invention.

While the present invention has been described in considerable detail with reference to certain preferred procedures, materials, and uses, it is understood that the class of lactones and their use as dispersing agents for gelatin is not limited thereto and that numerous variations and modifications described in the foregoing specification may be made. As for example, a mixture of two or more of the unsaturated lactones may be employed as dispersing agents.

It is also understood that all the broad examples of the present invention include the preparation of gelatin solutions in general, in which the gelatin is dispersed in the solvent by means of unsaturated lactones, or mixtures thereof. All such modifications and variations are within the scope of the invention as defined by the appended claims.

I claim:

1. A gelatin composition suitable for the subbing of a photographic film support, which comprises from 0.5% to 1.5% of gelatin dispersed in from 94.5% to 98.5% of a solvent for said support by m ns of from 0.05% to 1.0% of an unsaturated lactone selected from the class consisting of those of the following formulae:

0 130-91 HgO-Pl l) O and l O H O H =O H R It wherein R is a member selected from the class consisting of hydrogen and methyl group.

2. A gelatin composition suitable for the subbing of a photographic film support, which comprises from 0.5% to 1.5% of gelatin dispersed in from 94.5% to 98.5% of a solvent for said support by means of from 0.05% to 1.0% of I -angelica lactone.

3. A gelatin composition suitable for the subbing of a photographic film support, which comprises from 0.5% to 1.5% of gelatin dispersed in from 94.5% to 98.5% of a solvent for said support by means of from 0.05% to 1.0% of u-angelica lactone.

4. A gelatin composition suitable for the subbing of a photographic film support, which comprises from 0.5% to 1.5% of gelatin dispersed in from 94.5% to 98.5% of a solvent for said support by means of from 0.05% to 1.0% of A croton-olactone.

5. A gelatin composition suitable for the subbing of a cellulose derivative film support which comprises from 0.5% to 1.5% of gelatin dispersed in a mixture of 62.0% of acetone, 32.0% of methyl alcohol, and 2.0% of water, by means of from 0.05% to 1.0% of an unsaturated lactone selected from the class consisting of those of the following formulae:

wherein R is a member selected from the class consisting of hydrogen and methyl group.

6. A gelatin composition suitable for the subbing of a cellulose acetate photographic film support, which comprises 1.0% of gelatin dispersed in a mixture of 62.0% of acetone, 32.0% of methyl alwhol, and 2.0% of water, by means of 0.3% of ,B-angelica lactone.

'2'. A gelatin composition suitable for the subbing of a cellulose acetate-propionate photographic film support, which comprises 0.7% of gelatin dispersed in a mixture of 55.0% of acetone, 40.0% of methyl alcohol, and 2.1% of water, by means of 0.2% of a-angelica lactone.

8. A gelatin composition suitable for the subblue: of a poly(viny1chloride-vinyl acetate) film support, which comprises 1.0% of gelatin dispersed in a mixture of 53.0% of acetone, 40.0% of methyl alcohol, and 2.7% of water, by means of 0.3% of A-"-crotonolactone.

FRANK J. KASZUBA.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,313,570 Nadeau et a1 Mar. 9, 1943 2,341,877 Middleton et a1 Feb. 15, 1944 

